Ethylene-based polymer compositions and foams

ABSTRACT

The invention provides a composition comprising the following: A) a first polymer selected from the following: i) an ethylene/α-olefin interpolymer; or ii) an ethylene/α-olefin multi-block interpolymer; B) a second polymer selected from the following: iii) an ethylene/α-olefin interpolymer; iv) an ethylene/α-olefin/non-conjugated diene interpolymer; or v) an ethylene/α-olefin multi-block interpolymer; and wherein the first polymer has a density from 0.880 to 0.910 g/cc, and the second polymer has a density less than, or equal to, 0.867 g/cc, and wherein the weight ratio of the first polymer to the second polymer is from 0.5 to 9.

REFERENCE TO RELATED APPLICATIONS

The present application claims the benefit of U.S. ProvisionalApplication No. 61/694,287, filed Aug. 29, 2012.

BACKGROUND OF THE INVENTION

Cross-linked, closed-cell, foams formed from polyurethane (PU),ethylenevinyl acetate (EVA), or EVA/ethylene-alpha-olefin copolymerblends are commonly used for midsoles in footwear applications. Thefunction of the midsole is mainly cushioning, which helps to distribute,and soften, the force of impact when feet hit the ground. However, thedynamic properties of PU- and EVA-based foams change with temperature.These foams become too hard during cold weather, which results in lesscushioning effects. There is a need for new foam compositions thatprovide consistent dynamic properties (for example, constant storagemodulus (E′)) over a broad range of temperature, as compared toincumbent EVA- and PU-based foams.

International Publication WO 2011/079207 discloses a compositioncomprising at least the following: A) an ethylene/α-olefin/polyeneinterpolymer, B) an ethylene/α-olefin copolymer, C) optionally at leastone filler, D) at least one crosslinking agent, and E) at least oneblowing agent. The absolute difference in the solubility parametersbetween the polymer components is less than, or equal to, 0.15(cal/cm³)^(1/2).

U.S. Publication 2006/0211819 discloses polymer blends comprises thefollowing: 1) at least one ethylene/α-olefin interpolymer and 2) atleast one polyolefin, or at least one styrenic block copolymer, or acombination thereof. Such polyolefins include, but are not limited to,high melt strength, high density polyethylene, and high melt strengthpolypropylene. The ethylene/α-olefin interpolymers are random blockcopolymers, comprising at least a hard block and at least a soft block.The polyolefins can be homopolymers or interpolymers.

U.S. Publication 2008/0207786 discloses an ethylene-propylene-dienerubber foamed material, obtained by foaming a rubber compositioncontaining an ethylene-propylene-diene rubber, a quinoid cross-linkingagent, and an organic peroxide cross-linking agent.

U.S. Publication 2006/0199872 discloses foamable compositions and foams,comprising at least an ethylene/α-olefin interpolymer. The foam has adensity from greater than 150 to about 500 kg/m³. The foamablecompositions further comprise a blowing agent and a crosslinking agent.The ethylene/α-olefin interpolymer is a multi-block copolymer comprisingat least one soft block and at least one hard block.

U.S. Publication 2006/0199911 discloses a polymer composition comprisingat least an ethylene/α-olefin interpolymer and at least one otherpolymer. The other polymer can be selected from a secondethylene/α-olefin interpolymer, an elastomer, a polyolefin, a polarpolymer, and an ethylene/carboxylic acid interpolymer or ionomerthereof. The ethylene/α-olefin interpolymer is a block copolymer havingat least a hard block and at least a soft block.

Additional polymer formulations are disclosed in the followingreferences; U.S. Pat. Nos. 5,288,762, 6,221,964, 6,325,956, 6,340,717,6,384,096, 6,767,931, 7,557,147; U.S. Publications 2004/0039075,2004/0142405; International Publications WO 2011/163176, and WO2010/040019.

However, as discussed above, there remains a need for new foamcompositions that provide consistent dynamic properties (for example,constant storage modulus (E′)) over a broad range of temperature, ascompared to incumbent EVA- and PU-based foams. These needs have been metby the following invention.

SUMMARY OF THE INVENTION

The invention provides a composition comprising the following:

A) a first polymer selected from the following:

-   -   i) an ethylene/α-olefin interpolymer; or    -   ii) an ethylene/α-olefin multi-block interpolymer;

B) a second polymer selected from the following:

-   -   iii) an ethylene/α-olefin interpolymer;    -   iv) an ethylene/α-olefin/non-conjugated diene interpolymer; or    -   v) an ethylene/α-olefin multi-block interpolymer; and        wherein the first polymer has a density from 0.880 to 0.910        g/cc, and the second polymer has a density less than, or equal        to, 0.867 g/cc, and wherein the weight ratio of the first        polymer to the second polymer is from 0.5 to 9.

BRIEF DESCRIPTION OF THE DRAWINGS

FIG. 1 is a plot of “storage modulus (E′) versus temperature” forinventive and comparative foams.

DETAILED DESCRIPTION OF THE INVENTION

Applicant has discovered that the inventive compositions can be used toform foams that have consistent dynamic properties over a broad range oftemperature, and (ii) an elastic relaxation (measured as compression setat 50° C.) lower than 40%, which makes these materials better than theincumbent EVA- and PU-based foam over a wider temperature range.

As discussed above, the invention provides a composition comprising thefollowing:

A) a first polymer selected from the following:

-   -   i) an ethylene/α-olefin interpolymer, and further an        ethylene/α-olefin copolymer; or    -   ii) an ethylene/α-olefin multi-block interpolymer, and further        an ethylene/α-olefin multi-block copolymer;

B) a second polymer selected from the following:

-   -   iii) an ethylene/α-olefin interpolymer, and further an        ethylene/α-olefin copolymer;    -   iv) an ethylene/α-olefin/non-conjugated diene interpolymer; or    -   v) an ethylene/α-olefin multi-block interpolymer, and further an        ethylene/α-olefin multi-block copolymer; and wherein the first        polymer has a density from 0.880 to 0.910 g/cc, and the second        polymer has a density less than, or equal to, 0.867 g/cc, and        wherein the weight ratio of the first polymer to the second        polymer is from 0.5 to 9.

An inventive composition may comprise a combination of two or moreembodiments as described herein.

In one embodiment, the weight ratio of the first polymer to the secondpolymer is from 0.5 to 7, further from 0.6 to 4, and further from 0.7 to2.3.

In one embodiment, the first polymer has a density from 0.882 to 0.910g/cc, further from 0.885 to 0.910 g/cc, and further from 0.890 to 0.910g/cc (1 cc=1 cm³).

In one embodiment, the first polymer has a melt index (I2) from 0.1 to50 g/10 min, further from 0.5 to 20 g/10 min, further from 1 to 10 g/10min, and further from 1 to 7 g/10 min.

In one embodiment, the second polymer has a density from 0.855 to 0.867g/cc, further from 0.860 to 0.867 g/cc, and further from 0.863 to 0.867g/cc (1 cc=1 cm³).

In one embodiment, the second polymer has a melt index (I2) from 0.1 to20 g/10 min, further from 0.2 to 10 g/10 min, and further from 0.4 to 5g/5 min.

In one embodiment, the second polymer has a melt index (I2) less than,or equal to, 5 g/10 min, further less than, or equal to, 2 g/10 min.

In one embodiment, the second polymer has a melt index (I2) greaterthan, or equal to, 0.1 g/10 min, further greater than, or equal to, 0.2g/10 min.

In one embodiment, the first polymer has a melting temperature (Tm)greater than 70° C., as determined by DSC.

In one embodiment, the first polymer has a melting temperature (Tm) lessthan 130° C., as determined by DSC.

In one embodiment, the first polymer has a molecular weight distribution(Mw/Mn) from 1.2 to 3.

In one embodiment, the first polymer is i) an ethylene/α-olefininterpolymer, and further an ethylene/α-olefin copolymer.

In one embodiment, i) the ethylene/α-olefin interpolymer, and furtherethylene/α-olefin copolymer, has a melting temperature (Tm) greater than60° C., further greater than 70° C., and further greater than 80° C., asdetermined by DSC.

In one embodiment, i) the ethylene/α-olefin interpolymer, and furtherethylene/α-olefin copolymer, has a melting temperature (Tm) less than120° C., further less than 110° C., and further less than 100° C., asdetermined by DSC.

In one embodiment, i) the ethylene/α-olefin interpolymer, and furtherethylene/α-olefin copolymer, has a molecular weight distribution (Mw/Mn)from 1.2 to 3.5, further from 1.5 to 3.0, and further from 1.7 to 2.5.

In one embodiment, i) the ethylene/α-olefin interpolymer, and furtherethylene/α-olefin copolymer, is a homogeneously branched linearethylene/α-olefin interpolymer, or a homogeneously branchedsubstantially linear ethylene/α-olefin interpolymer.

In one embodiment, i) the ethylene/α-olefin interpolymer is ahomogeneously branched linear ethylene/α-olefin interpolymer.

In one embodiment, i) the ethylene/α-olefin interpolymer is ahomogeneously branched substantially linear ethylene/α-olefininterpolymer.

In one embodiment, i) the ethylene/α-olefin copolymer is a homogeneouslybranched substantially linear ethylene/α-olefin copolymer.

In one embodiment, i) the ethylene/α-olefin copolymer is a homogeneouslybranched linear ethylene/α-olefin copolymer.

In one embodiment, the first polymer is ii) an olefin blockinterpolymer, and further an olefin block copolymer.

In one embodiment, the second polymer has a molecular weightdistribution (Mw/Mn) from 1.2 to 3.

In one embodiment, the second polymer is iii) an ethylene/α-olefininterpolymer, and further an ethylene/α-olefin copolymer.

In one embodiment, iii) the ethylene/α-olefin interpolymer, and furtherethylene/α-olefin copolymer, has a molecular weight distribution (Mw/Mn)from 1.2 to 3.5, further from 1.5 to 3.0, and further from 1.7 to 2.5.

In one embodiment, iii) the ethylene/α-olefin interpolymer, and furtherethylene/α-olefin copolymer, has a melting temperature (Tm) greater than20° C., further greater than 30° C., and further greater than 40° C., asdetermined by DSC.

In one embodiment, iii) the ethylene/α-olefin interpolymer, and furtherethylene/α-olefin copolymer, has a melting temperature (Tm) less than80° C., further less than 70° C., and further less than 60° C., asdetermined by DSC.

In one embodiment, iii) the ethylene/α-olefin interpolymer is ahomogeneously branched linear ethylene/α-olefin interpolymer, or ahomogeneously branched substantially linear ethylene/α-olefininterpolymer.

In one embodiment, iii) the ethylene/α-olefin interpolymer is ahomogeneously branched linear ethylene/α-olefin interpolymer.

In one embodiment, iii) the ethylene/α-olefin interpolymer is ahomogeneously branched substantially linear ethylene/α-olefininterpolymer.

In one embodiment, iii) the ethylene/α-olefin copolymer is ahomogeneously branched linear ethylene/α-olefin copolymer, or ahomogeneously branched substantially linear ethylene/α-olefin copolymer.

In one embodiment, iii) the ethylene/α-olefin copolymer is ahomogeneously branched linear ethylene/α-olefin copolymer.

In one embodiment, iii) the ethylene/α-olefin copolymer is ahomogeneously branched substantially linear ethylene/α-olefin copolymer.

In one embodiment, the second polymer is iv) anethylene/α-olefin/non-conjugated diene interpolymer.

In one embodiment, iv) the ethylene/α-olefin/non-conjugated dieneinterpolymer has a Mooney Viscosity (ML 1+4) at 125° C., from 5 to 70,further from 10 to 60, and further from 15 to 50.

In one embodiment, iv) the ethylene/α-olefin/non-conjugated dieneinterpolymer has a Mooney Viscosity (ML 1+4) at 125° C., from 5 to 50,further from 10 to 40, and further from 15 to 30.

In one embodiment, the second polymer is v) an olefin blockinterpolymer, and further an olefin block copolymer.

In one embodiment, the composition comprising the following: Ai) anethylene/α-olefin interpolymer, and further a copolymer; and B) a secondpolymer selected from the following:

-   -   iii) an ethylene/α-olefin interpolymer, and further a copolymer;    -   iv) an ethylene/α-olefin/non-conjugated diene interpolymer; or    -   v) an ethylene/α-olefin multi-block interpolymer, and further a        copolymer.

In one embodiment, the composition comprising the following: Ai) anethylene/α-olefin interpolymer, and further a copolymer; and B) a secondpolymer selected from the following:

-   -   iii) an ethylene/α-olefin interpolymer, and further a copolymer;        or    -   iv) an ethylene/α-olefin/non-conjugated diene interpolymer.

In one embodiment, the composition comprising the following: Ai) anethylene/α-olefin interpolymer, and further a copolymer; and B) a secondpolymer selected from the following:

-   -   iii) an ethylene/α-olefin interpolymer, and further a copolymer;        or    -   v) an ethylene/α-olefin multi-block interpolymer, and further a        copolymer.

In one embodiment, the composition comprising the following: Ai) anethylene/α-olefin interpolymer, and further a copolymer; and B) a secondpolymer selected from the following:

-   -   iv) an ethylene/α-olefin/non-conjugated diene interpolymer; or    -   v) an ethylene/α-olefin multi-block interpolymer, and further a        copolymer.

In one embodiment, the composition comprising the following: Aii) anethylene/α-olefin multi-block interpolymer, and further a copolymer; andB) a second polymer selected from the following:

-   -   iii) an ethylene/α-olefin interpolymer, and further a copolymer;    -   iv) an ethylene/α-olefin/non-conjugated diene interpolymer; or    -   v) an ethylene/α-olefin multi-block interpolymer, and further a        copolymer.

In one embodiment, the composition comprising the following: Aii) anethylene/α-olefin multi-block interpolymer, and further a copolymer; andB) a second polymer selected from the following:

-   -   iii) an ethylene/α-olefin interpolymer, and further a copolymer;        or    -   iv) an ethylene/α-olefin/non-conjugated diene interpolymer.

In one embodiment, the composition comprising the following: Aii) anethylene/α-olefin multi-block interpolymer, and further a copolymer; andB) a second polymer selected from the following:

-   -   iii) an ethylene/α-olefin interpolymer, and further a copolymer;        or    -   v) an ethylene/α-olefin multi-block interpolymer, and further a        copolymer.

In one embodiment, the composition comprising the following: Aii) anethylene/α-olefin multi-block interpolymer, and further a copolymer; andB) a second polymer selected from the following:

-   -   iv) an ethylene/α-olefin/non-conjugated diene interpolymer; or    -   v) an ethylene/α-olefin multi-block interpolymer, and further a        copolymer.

In one embodiment, the composition further comprises a free radicalagent and a foaming agent.

In one embodiment, Component A is present in an amount from 40 to 90weight percent, further from 40 to 80 weight percent, and further from40 to 70 weight percent, and Component B is present in an amount from 60to 10 weight percent, further from 60 to 20 weight percent, and furtherfrom 60 to 30 weight percent, and wherein the weight percentages ofComponents A and B are each based on the sum weight of Components A andB.

In one embodiment, Component A is present in an amount from 50 to 80weight percent, further from 55 to 80 weight percent, and Component B ispresent in an amount from 50 to 20 weight percent, further from 45 to 20weight percent, and wherein the weight percentages of Components A and Bare each based on the sum weight of Components A and B.

In one embodiment, Component A is present in an amount from 50 to 70weight percent, further from 55 to 70 weight percent, and Component B ispresent in an amount from 50 to 30 weight percent, further from 45 to 30weight percent, and wherein the weight percentages of Components A and Bare each based on the sum weight of Components A and B.

In one embodiment, the composition comprises greater than, or equal to,50 weight percent components A and B, based on the weight of thecomposition.

In one embodiment, the composition comprises greater than, or equal to,70 weight percent components A and B, based on the weight of thecomposition.

In one embodiment, the composition comprises greater than, or equal to,80 weight percent components A and B, based on the weight of thecomposition.

In one embodiment, the composition comprises greater than, or equal to,88 weight percent components A and B, based on the weight of thecomposition.

In one embodiment, the composition comprises less than 5 weight percent,further less than 2 weight percent, and further less than 1 weightpercent, of a propylene-based polymer, based on the weight of thecomposition.

In one embodiment, the composition does not contain a propylene-basedpolymer.

In one embodiment, the composition comprises less than 5 weight percent,further less than 2 weight percent, and further less than 1 weightpercent, of a polypropylene homopolymer, based on the weight of thecomposition.

In one embodiment, the composition does not contain a polypropylenehomopolymer.

In one embodiment, the composition comprises less than 2 weight percent,further less than 1 weight percent, further less than 0.5 weightpercent, and further less than 0.1 weight percent, of an oil, based onthe weight of the composition.

In one embodiment, the composition does not contain an oil.

In one embodiment, the composition comprises less than 5 weight percent,further less than 2 weight percent, and further less than 1 weightpercent, of an acrylic-modified polytetrafluoroethylene, based on theweight of the composition.

In one embodiment, the composition does not contain an acrylic-modifiedpolytetrafluoroethylene.

In one embodiment, the composition does not contain a poly(sulfonylazide).

An inventive composition may comprise a combination of two or moreembodiments as described herein.

The first polymer of Component A may comprise a combination of two ormore embodiments as described herein.

The second polymer of Component B may comprise a combination of two ormore embodiments as described herein.

The invention also provides a foam formed from an inventive compositiondescribed herein. In a further embodiment, the foam has a density from150 to 400 kg/m³, further from 200 to 350 kg/m³, and further from 250 to300 kg/m³.

The invention also provides a crosslinked composition formed from aninventive composition described herein.

The invention also provides an article comprising at least one componentformed from an inventive composition described herein.

The invention also provides a process to form a foam, said processcomprising extruding an inventive composition described herein.

An inventive composition may comprise a combination of two or moreembodiments as described herein.

An inventive foam may comprise a combination of two or more embodimentsas described herein.

An inventive crosslinked composition may comprise a combination of twoor more embodiments as described herein.

An inventive article may comprise a combination of two or moreembodiments as described herein.

An inventive process may comprise a combination of two or moreembodiments as described herein.

First Ethylene-Based Polymer (Component A)

The first ethylene-based polymer is an ethylene/α-olefin interpolymer,and further an ethylene/α-olefin copolymer, or an ethylene/α-olefinmulti-block interpolymer, and further a copolymer.

Ethylene/α-Olefin Interpolymers (Component A)

Ethylene/α-olefin interpolymers include polymers formed by polymerizingethylene with one or more, and preferably one, C3-C10 α-olefin(s).Illustrative α-olefins include propylene, 1-butene, 1-pentene, 1-hexene,4-methyl-1-pentene, 1-heptene, 1-octene, 1-nonene and 1-decene.Preferably, the α-olefin is propylene, 1-butene, 1-hexene or 1-octene.Preferred copolymers include ethylene/propylene (EP) copolymers,ethylene/butene (EB) copolymers, ethylene/hexene (EH) copolymers,ethylene/octene (EO) copolymers.

Commercial examples of suitable ethylene/α-olefin interpolymers includeENGAGE Polyolefin Elastomers available from The Dow Chemical Company;EXCEED and EXACT polymers available from ExxonMobil Chemical Company;and TAFMER polymers available from the Mitsui Chemical Company.

In one embodiment, the ethylene/α-olefin interpolymer, and further acopolymer, has a melting point (Tm) greater than 40° C. preferablygreater than 50° C., more preferably greater than 60° C., as determinedby DSC.

In one embodiment, the ethylene/α-olefin interpolymer, and further acopolymer, has a melting point (Tm) less than 120° C., preferably lessthan 110° C., and more preferably less than 100° C., as determined byDSC.

In one embodiment, the ethylene/α-olefin interpolymer, and further acopolymer, has a density greater than, or equal to, 0.868 g/cc, furthergreater than, or equal to, 0.870 g/cc, further greater than, or equalto, 0.875 g/cc.

In one embodiment, the ethylene/α-olefin interpolymer, and further acopolymer, has a density less than, or equal to, 0.910 g/cc, furtherless than, or equal to, 0.905 g/cc, add further less than, or equal to,0.900 g/cc.

In one embodiment, the ethylene/α-olefin interpolymer, and further acopolymer, has a melt index (I2) greater than, or equal to, 0.1 g/10min, further greater than, or equal to, 0.2 g/10 min, add furthergreater than, or equal to, 0.5 g/10 min.

In one embodiment, the ethylene/α-olefin interpolymer, and further acopolymer, has a melt index (I2) less than, or equal to, 50 g/10 min,further less than, or equal to, 20 g/10 min, and further less than, orequal to, 10 g/10 min.

In one embodiment, the ethylene/α-olefin interpolymer, and further acopolymer, has a melt index (I2) from 0.1 g/10 min to 50 g/10 min,further from 0.2 g/10 min to 20 g/10 min, add further from 0.5 g/10 minto 10 g/10 min.

In one embodiment, the ethylene/α-olefin interpolymer, and further acopolymer, has molecular weight distribution (Mw/Mn) from 1.2 to 3.5,further from 1.5 to 3.0, and further from 1.7 to 2.5, as determined byGPC.

In one embodiment, the ethylene/α-olefin interpolymer, and further acopolymer, has a percent crystallinity of less than, or equal to, 50percent, further less than, or equal to, 40 percent, and further lessthan, or equal to, 30 percent, as measured by DSC.

In one embodiment, the ethylene/α-olefin interpolymer, and further acopolymer, has a percent crystallinity of greater than, or equal to, 2percent, further greater than, or equal to, 5 percent, and furthergreater than, or equal to, 10 percent, as measured by DSC.

In one embodiment, the ethylene/α-olefin interpolymer, and furtherethylene/α-olefin copolymer, has a melting temperature (Tm) greater than60° C., further greater than 70° C., and further greater than 80° C., asdetermined by DSC.

In one embodiment, the ethylene/α-olefin interpolymer, and furtherethylene/α-olefin copolymer, has a melting temperature (Tm) less than120° C., further less than 110° C., and further less than 100° C., asdetermined by DSC.

In one embodiment, the ethylene/α-olefin interpolymer is a homogeneouslybranched linear interpolymer, and further a copolymer, or a homogeneousbranched substantially linear interpolymer, and further a copolymer.

The terms “homogeneous” and “homogeneously-branched” are used inreference to an ethylene/α-olefin interpolymer, in which the α-olefincomonomer is randomly distributed within a given polymer molecule, andall of the polymer molecules have the same or substantially the samecomonomer-to-ethylene ratio. See discussion below.

In one embodiment, the ethylene/α-olefin interpolymer, and furthercopolymer, is a homogeneously branched linear interpolymer, and furthercopolymer.

In one embodiment, the ethylene/α-olefin interpolymer, and furthercopolymer, is a homogeneous branched substantially linear interpolymer,and further copolymer.

The homogeneously branched linear ethylene interpolymers are ethylenepolymers, which lack long chain branching, but do have short chainbranches, derived from the comonomer polymerized into the interpolymer,and which are homogeneously distributed, both within the same polymerchain, and between different polymer chains. These ethylene/α-olefininterpolymers have a linear polymer backbone, no measurable long chainbranching, and a narrow molecular weight distribution. This class ofpolymers is disclosed, for example, by Elston in U.S. Pat. No.3,645,992, and subsequent processes to produce such polymers, usingbis-metallocene catalysts, have been developed, as shown, for example,in EP 0 129 368; EP 0 260 999; U.S. Pat. No. 4,701,432; U.S. Pat. No.4,937,301; U.S. Pat. No. 4,935,397; U.S. Pat. No. 5,055,438; and WO90/07526; each incorporated herein by reference. As discussed, thehomogeneously branched linear ethylene interpolymers lack long chainbranching, just as is the case for the linear low density polyethylenepolymers or linear high density polyethylene polymers. Commercialexamples of homogeneously branched linear ethylene/α-olefininterpolymers include TAFMER polymers from the Mitsui Chemical Company,and EXACT and EXCEED polymers from ExxonMobil Chemical Company.

The substantially linear ethylene/α-olefin interpolymers have long chainbranching. The long chain branches have the same comonomer distributionas the polymer backbone, and can have about the same length as thelength of the polymer backbone. “Substantially linear,” typically, is inreference to a polymer that is substituted, on average, with “0.01 longchain branches per 1000 carbons” to “3 long chain branches per 1000carbons.” The length of a long chain branch is longer than the carbonlength of a short chain branch, formed from the incorporation of onecomonomer into the polymer backbone. For example, see U.S. Pat. Nos.5,272,236; 5,278,272; each incorporated herein by reference.

The substantially linear ethylene/α-olefin interpolymers form a uniqueclass of homogeneously branched ethylene polymers. They differsubstantially from the well-known class of conventional, homogeneouslybranched linear ethylene/α-olefin interpolymers, as discussed above,and, moreover, they are not in the same class as conventionalheterogeneous “Ziegler-Natta catalyst polymerized” linear ethylenepolymers (for example, ultra low density polyethylene (ULDPE), linearlow density polyethylene (LLDPE) or high density polyethylene (HDPE),made, for example, using the technique disclosed by Anderson et al., inU.S. Pat. No. 4,076,698); nor are they in the same class as highpressure, free-radical initiated, highly branched polyethylenes, suchas, for example, low density polyethylene (LDPE), ethylene-acrylic acid(EAA) copolymers and ethylene vinyl acetate (EVA) copolymers.

The homogeneously branched, substantially linear ethylene/α-olefininterpolymers useful in the invention have excellent processability,even though they have a relatively narrow molecular weight distribution.Long chain branching can be determined by using 13C Nuclear MagneticResonance (NMR) spectroscopy, and can be quantified using the method ofRandall (Rev. Macromol. Chem. Phys., C29 (2 &3), 1989, p. 285-297), thedisclosure of which is incorporated herein by reference. Two othermethods are Gel Permeation Chromatography, couple with a Low Angle LaserLight Scattering detector (GPCLALLS), and Gel Permeation Chromatography,coupled with a Differential Viscometer detector (GPC-DV). The use ofthese techniques for long chain branch detection, and the underlyingtheories, have been well documented in the literature. See, for example,Zimm, B. H. and Stockmayer, W. H., J. Chem. Phys., 17, 1301 (1949) andRudin, A., Modern Methods of Polymer Characterization, John Wiley &Sons, New York (1991) pp. 103-112.

In contrast to “substantially linear ethylene polymer,” “linear ethylenepolymer” means that the polymer lacks measurable or demonstrable longchain branches, that is, the polymer is substituted with an average ofless than 0.01 long chain branch per 1000 carbons.

The ethylene/α-olefin interpolymer may comprise a combination of two ormore embodiments as described herein.

The ethylene/α-olefin copolymer may comprise a combination of two ormore embodiments as described herein.

Ethylene/α-Olefin Multi-Block Interpolymers (Component A)

In one embodiment, the first polymer is an ethylene/α-olefin multi-blockinterpolymer, and further an ethylene/α-olefin multi-block copolymer.

In a preferred embodiment, the ethylene/α-olefin multi-blockinterpolymer, and further an ethylene/α-olefin multi-block copolymer,comprises a majority amount of polymerized ethylene, based on the weightof the polymer.

The term “olefin block copolymer” or “OBC” means an ethylene/α-olefinmulti-block copolymer and includes ethylene and one or morecopolymerizable α-olefin comonomer in polymerized form, characterized bymultiple blocks or segments of two or more polymerized monomer unitsdiffering in chemical or physical properties. When referring to amountsof “ethylene” or “comonomer” in the copolymer, it is understood thatthis means polymerized units thereof. In some embodiments, themulti-block copolymer can be represented by the following formula:(AB)_(n),where n is at least 1, preferably an integer greater than 1, such as 2,3, 4, 5, 10, 15, 20, 30, 40, 50, 60, 70, 80, 90, 100, or higher, “A”represents a hard block or segment and “B” represents a soft block orsegment. Preferably, As and Bs are linked in a substantially linearfashion, as opposed to a substantially branched or substantiallystar-shaped fashion. In other embodiments, A blocks and B blocks arerandomly distributed along the polymer chain. In other words, the blockcopolymers usually do not have a structure as follows.

-   -   AAA-AA-BBB-BB.

In still other embodiments, the block copolymers do not usually have athird type of block, which comprises different comonomer(s). In yetother embodiments, each of block A and block B has monomers orcomonomers substantially randomly distributed within the block. In otherwords, neither block A nor block B comprises two or more sub-segments(or sub-blocks) of distinct composition, such as a tip segment, whichhas a substantially different composition than the rest of the block.

Preferably, ethylene comprises the majority mole fraction of the wholeblock copolymer, i.e., ethylene comprises at least 50 mole percent ofthe whole polymer. More preferably ethylene comprises at least 60 molepercent, at least 70 mole percent, or at least 80 mole percent, with thesubstantial remainder of the whole polymer comprising at least one othercomonomer that is preferably an α-olefin having 3 or more carbon atoms.In some embodiments, the olefin block copolymer may comprise 50 mol % to90 mol % ethylene, preferably 60 mol % to 85 mol %, more preferably 65mol % to 80 mol %. For many ethylene/octene block copolymers, thepreferred composition comprises an ethylene content greater than 80 molepercent of the whole polymer and an octene content of from 10 to 15,preferably from 15 to 20 mole percent of the whole polymer.

The olefin block copolymer includes various amounts of “hard” and “soft”segments. “Hard” segments are blocks of polymerized units in whichethylene is present in an amount greater than 95 weight percent, orgreater than 98 weight percent based on the weight of the polymer, up to100 weight percent. In other words, the comonomer content (content ofmonomers other than ethylene) in the hard segments is less than 5 weightpercent, or less than 2 weight percent based on the weight of thepolymer, and can be as low as zero. In some embodiments, the hardsegments include all, or substantially all, units derived from ethylene.“Soft” segments are blocks of polymerized units in which the comonomercontent (content of monomers other than ethylene) is greater than 5weight percent, or greater than 8 weight percent, greater than 10 weightpercent, or greater than 15 weight percent based on the weight of thepolymer. In some embodiments, the comonomer content in the soft segmentscan be greater than 20 weight percent, greater than 25 weight percent,greater than 30 weight percent, greater than 35 weight percent, greaterthan 40 weight percent, greater than 45 weight percent, greater than 50weight percent, or greater than 60 weight percent and can be up to 100weight percent.

The soft segments can be present in an OBC from 1 weight percent to 99weight percent of the total weight of the OBC, or from 5 weight percentto 95 weight percent, from 10 weight percent to 90 weight percent, from15 weight percent to 85 weight percent, from 20 weight percent to 80weight percent, from 25 weight percent to 75 weight percent, from 30weight percent to 70 weight percent, from 35 weight percent to 65 weightpercent, from 40 weight percent to 60 weight percent, or from 45 weightpercent to 55 weight percent of the total weight of the OBC. Conversely,the hard segments can be present in similar ranges. The soft segmentweight percentage and the hard segment weight percentage can becalculated based on data obtained from DSC or NMR. Such methods andcalculations are disclosed in, for example, U.S. Pat. No. 7,608,668,entitled “Ethylene/α-Olefin Block Inter-polymers,” filed on Mar. 15,2006, in the name of Cohn L. P. Shan, Lonnie Hazlitt, et. al. andassigned to Dow Global Technologies Inc., the disclosure of which isincorporated by reference herein in its entirety. In particular, hardand soft segment weight percentages and comonomer content may bedetermined as described in Column 57 to Column 63 of U.S. Pat. No.7,608,668.

The olefin block copolymer is a polymer comprising two or morechemically distinct regions or segments (referred to as “blocks”)preferably joined in a linear manner, that is, a polymer comprisingchemically differentiated units which are joined end-to-end with respectto polymerized ethylenic functionality, rather than in pendent orgrafted fashion. In an embodiment, the blocks differ in the amount ortype of incorporated comonomer, density, amount of crystallinity,crystallite size attributable to a polymer of such composition, type ordegree of tacticity (isotactic or syndiotactic), regio-regularity orregio-irregularity, amount of branching (including long chain branchingor hyper-branching), homogeneity or any other chemical or physicalproperty. Compared to block interpolymers of the prior art, includinginterpolymers produced by sequential monomer addition, fluxionalcatalysts, or anionic polymerization techniques, the present OBC ischaracterized by unique distributions of both polymer polydispersity(PDI or Mw/Mn or MWD), block length distribution, and/or block numberdistribution, due, in an embodiment, to the effect of the shuttlingagent(s) in combination with multiple catalysts used in theirpreparation.

In an embodiment, the OBC is produced in a continuous process andpossesses a polydispersity index, PDI (or MWD), from 1.7 to 3.5, or from1.8 to 3, or from 1.8 to 2.5, or from 1.8 to 2.2. When produced in abatch or semi-batch process, the OBC possesses PDI from 1.0 to 3.5, orfrom 1.3 to 3, or from 1.4 to 2.5, or from 1.4 to 2.

In addition, the olefin block copolymer possesses a PDI fitting aSchultz-Flory distribution rather than a Poisson distribution. Thepresent OBC has both a polydisperse block distribution as well as apolydisperse distribution of block sizes. This results in the formationof polymer products having improved and distinguishable physicalproperties. The theoretical benefits of a polydisperse blockdistribution have been previously modeled and discussed in Potemkin,Physical Review E (1998) 57 (6), pp. 6902-6912, and Dobrynin, J. Chem.Phvs. (1997) 107 (21), pp 9234-9238.

In an embodiment, the present olefin block copolymer possesses a mostprobable distribution of block lengths. In an embodiment, the olefinblock copolymer is defined as having:

(A) Mw/Mn from 1.7 to 3.5, at least one melting point, Tm, in degreesCelsius, and a density, d, in grams/cubic centimeter, where in thenumerical values of Tm and d correspond to the relationship:Tm>−2002.9+4538.5(d)−2422.2(d)², and/or

(B) Mw/Mn from 1.7 to 3.5, and is characterized by a heat of fusion, ΔHin J/g, and a delta quantity, ΔT, in degrees Celsius defined as thetemperature difference between the tallest DSC peak and the tallestCrystallization Analysis Fractionation (“CRYSTAF”) peak, wherein thenumerical values of ΔT and ΔH have the following relationships:ΔT>−0.1299ΔH+62.81 for ΔH greater than zero and up to 130 J/g,ΔT≧48° C. for ΔH greater than 130 J/g,wherein the CRYSTAF peak is determined using at least 5 percent of thecumulative polymer, and if less than 5 percent of the polymer has anidentifiable CRYSTAF peak, then the CRYSTAF temperature is 30° C.;and/or

(C) elastic recovery, Re, in percent at 300 percent strain and 1 cyclemeasured with a compression-molded film of the ethylene/α-olefininterpolymer, and has a density, d, in grams/cubic centimeter, whereinthe numerical values of Re and d satisfy the following relationship whenethylene/α-olefin interpolymer is substantially free of crosslinkedphase:Re>1481−1629(d); and/or

(D) has a molecular fraction which elutes between 40° C. and 130° C.when fractionated using TREF, characterized in that the fraction has amolar comonomer content greater than, or equal to, the quantity(−0.2013) T+20.07, more preferably greater than or equal to the quantity(−0.2013) T+21.07, where T is the numerical value of the peak elutiontemperature of the TREF fraction, measured in ° C.; and/or,

(E) has a storage modulus at 25° C., G′ (25° C.), and a storage modulusat 100° C., G′(100° C.), wherein the ratio of G′ (25° C.) to G′ (100°C.) is in the range of 1:1 to 9:1.

The olefin block copolymer may also have:

(F) a molecular fraction which elutes between 40° C. and 130° C. whenfractionated using TREF, characterized in that the fraction has a blockindex of at least 0.5 and up to 1 and a molecular weight distribution,Mw/Mn, greater than 1.3; and/or

(G) average block index greater than zero and up to 1.0 and a molecularweight distribution, Mw/Mn greater than 1.3. It is understood that theolefin block copolymer may have one, some, all, or any combination ofproperties (A)-(G). Block Index can be determined as described in detailin U.S. Pat. No. 7,608,668 herein incorporated by reference for thatpurpose. Analytical methods for determining properties (A) through (G)are disclosed in, for example, U.S. Pat. No. 7,608,668, Col. 31, line 26through Col. 35, line 44, which is herein incorporated by reference forthat purpose.

The ethylene/α-olefin multi-block interpolymer, and further copolymer,may comprise any one of properties (A) through (G), or may comprises acombination of two or more of (A) through (G).

Suitable monomers for use in preparing the present OBC include ethyleneand one or more addition polymerizable monomers other than ethylene.Examples of suitable comonomers include straight-chain or branchedα-olefins of 3 to 30, preferably 3 to 20, carbon atoms, such aspropylene, 1-butene, 1-pentene, 3-methyl-1-butene, 1-hexene,4-methyl-1-pentene, 3-methyl-1-pentene, 1-octene, 1-decene, 1-dodecene,1-tetradecene, 1-hexadecene, 1-octadecene and 1-eicosene; cyclo-olefinsof 3 to 30, preferably 3 to 20, carbon atoms, such as cyclopentene,cycloheptene, norbornene, 5-methyl-2-norbornene, tetracyclododecene, and2-methyl-1,4,5,8-dimethano-1,2,3,4,4a,5,8,8a-octahydro-naphthalene; di-and polyolefins, such as butadiene, isoprene, 4-methyl-1,3-pentadiene,1,3-pentadiene, 1,4-pentadiene, 1,5-hexadiene, 1,4-hexadiene,1,3-hexadiene, 1,3-octadiene, 1,4-octadiene, 1,5-octadiene,1,6-octadiene, 1,7-octadiene, ethylidenenorbornene, vinyl norbornene,dicyclopentadiene, 7-methyl-1,6-octadiene,4-ethylidene-8-methyl-1,7-nonadiene, and 5,9-dimethyl-1,4,8-decatriene;and 3-phenylpropene, 4-phenylpropene, 1,2-difluoroethylene,tetrafluoroethylene, and 3,3,3-trifluoro-1-propene. Preferred α-olefinsinclude, but are not limited to, C3-C20 α-olefins, and preferably C3-C10α-olefins. More preferred α-olefins include propylene, 1-butene,1-pentene, 1-hexene, 1-heptene and 1-octene, and more preferably includepropylene, 1-butene, 1-hexene and 1-octene.

The olefin block copolymers can be produced via a chain shuttlingprocess such as described in U.S. Pat. No. 7,858,706, which is hereinincorporated by reference. In particular, suitable chain shuttlingagents and related information are listed in Col. 16, line 39 throughCol. 19, line 44. Suitable catalysts are described in Col. 19, line 45through Col. 46, line 19 and suitable co-catalysts in Col. 46, line 20through Col. 51 line 28. The process is described throughout thedocument, but particularly in Col. Col 51, line 29 through Col. 54, line56. The process is also described, for example, in the following: U.S.Pat. No. 7,608,668; U.S. Pat. No. 7,893,166; and U.S. Pat. No.7,947,793.

In one embodiment, the ethylene/α-olefin multi-block interpolymer, andfurther copolymer, has a density of less than, or equal to, 0.910 g/cc,further less than, or equal to, 0.905 g/cc, further less than, or equalto, 0.900 g/cc, and further less than, or equal to, 0.885 g/cc.

In one embodiment, the ethylene/α-olefin multi-block interpolymer, andfurther copolymer, has a density greater than, or equal to, 0.882 g/cc,further greater than, or equal to, 0.885 g/cc, and further greater than,or equal to, 0.887 g/cc. Density is measured by the procedure of ASTMD-792-08.

In one embodiment, the ethylene/α-olefin multi-block interpolymer, andfurther copolymer, has a melting point of greater than 90° C., furthergreater than 100° C. The melting point is measured by DifferentialScanning calorimetry (DSC) method described in U.S. Publication2006/0199930 (WO 2005/090427), incorporated herein by reference.

In one embodiment, the ethylene/α-olefin multi-block interpolymer, andfurther copolymer, has a melt index (I2) greater than, or equal to, 0.1g/10 min, further greater than, or equal to, 0.5 g/10 min, and furthergreater than, or equal to, 1 g/10 min, as determined using ASTM D-1238(190° C., 2.16 kg load).

In one embodiment, the ethylene/α-olefin multi-block interpolymer, andfurther copolymer, has a melt index (I2) less than, or equal to, 50 g/10min, further less than, or equal to, 20 g/10 min, and further less than,or equal to, 10 g/10 min, as determined using ASTM D-1238 (190° C., 2.16kg load).

An ethylene/α-olefin multi-block interpolymer may comprise a combinationof two or more embodiments as described herein.

An ethylene/α-olefin multi-block copolymer may comprise a combination oftwo or more embodiments as described herein.

Second Ethylene-Based Polymer (Component B)

The second ethylene-based polymer is an ethylene/α-olefin interpolymer,and further a copolymer, or an ethylene/α-olefin/diene interpolymer, oran or an ethylene/α-olefin multi-block interpolymer, and further acopolymer.

Ethylene/α-Olefin Interpolymers (Component B)

Ethylene/α-olefin interpolymers, further copolymers, include polymersformed by polymerizing ethylene with one or more, and preferably one,C3-C10 α-olefin(s). Illustrative α-olefins include propylene, 1-butene,1-pentene, 1-hexene, 4-methyl-1-pentene, 1-heptene, 1-octene, 1-noneneand 1-decene. Preferably, the α-olefin is propylene, 1-butene, 1-hexeneor 1-octene. Preferred copolymers include ethylene/propylene (EP)copolymers, ethylene/butene (EB) copolymers, ethylene/hexene (EH)copolymers, ethylene/octene (EO) copolymers.

Commercial examples of suitable ethylene/α-olefin interpolymers includeENGAGE Polyolefin Elastomers available from The Dow Chemical Company;EXCEED and EXACT polymers available from ExxonMobil Chemical Company;and TAFMER polymers available from the Mitsui Chemical Company.

In one embodiment, the ethylene/α-olefin interpolymer, furthercopolymer, has a melting point (Tm) greater than 20° C. further greaterthan 30° C., and further greater than 40° C., as determined by DSC.

In one embodiment, the ethylene/α-olefin interpolymer, furthercopolymer, has a melting point (Tm) less than 70° C., further less than80° C., and further less than 60° C., as determined by DSC.

In one embodiment, the ethylene/α-olefin interpolymer, furthercopolymer, has a density greater than, or equal to, 0.850 g/cc, furthergreater than, or equal to, 0.855 g/cc, and further greater than, orequal to, 0.860 g/cc.

In one embodiment, the ethylene/α-olefin interpolymer, furthercopolymer, has a density less than, or equal to, 0.867 g/cc, furtherless than, or equal to, 0.866 g/cc, and further less than, or equal to,0.865 g/cc.

In one embodiment, the ethylene/α-olefin interpolymer, furthercopolymer, has a melt index (I2) greater than, or equal to, 0.1 g/10min, further greater than, or equal to, 0.2 g/10 min, and furthergreater than, or equal to, 0.4 g/10 min.

In one embodiment, the ethylene/α-olefin interpolymer, furthercopolymer, has a melt index (I2) less than, or equal to, 10 g/10 min,further less than, or equal to, 5 g/10 min, and further less than, orequal to, 2 g/10 min.

In one embodiment, the ethylene/α-olefin interpolymer, furthercopolymer, has a melt index (I2) from 0.1 g/10 min to 10 g/10 min,further from 0.2 g/10 min to 5 g/10 min, and further from 0.4 g/10 minto 2 g/10 min.

In one embodiment, the ethylene/α-olefin interpolymer, furthercopolymer, has molecular weight distribution (Mw/Mn) from 1.2 to 3.5,further from 1.5 to 3.0, and further from 1.7 to 2.5, as determined byGPC.

In one embodiment, the ethylene/α-olefin interpolymer, furthercopolymer, has a percent crystallinity of less than, or equal to, 30percent, further less than, or equal to, 20 percent, and further lessthan, or equal to, 15 percent, as measured by DSC.

In one embodiment, the ethylene/α-olefin interpolymer, furthercopolymer, has a percent crystallinity of greater than, or equal to, 1percent, further greater than, or equal to, 2 percent as measured byDSC.

In one embodiment, the ethylene/α-olefin interpolymer, furthercopolymer, is a homogeneously branched linear copolymer, or ahomogeneous branched substantially linear interpolymer, furthercopolymer.

In one embodiment, the ethylene/α-olefin interpolymer, furthercopolymer, is a homogeneously branched linear interpolymer, furthercopolymer.

In one embodiment, the ethylene/α-olefin interpolymer, furthercopolymer, is a homogeneously branched substantially linearinterpolymer, further copolymer.

The terms “homogeneous” and “homogeneously-branched” are used inreference to an ethylene/α-olefin interpolymer, in which the α-olefincomonomer is randomly distributed within a given polymer molecule, andall of the polymer molecules have the same or substantially the samecomonomer-to-ethylene ratio. See discussion above.

An ethylene/α-olefin interpolymer may comprise a combination of two ormore embodiments as described herein.

An ethylene/α-olefin copolymer may comprise a combination of two or moreembodiments as described herein.

Ethylene/α-Olefin/Diene Interpolymers (Component B)

The ethylene/α-olefin/diene interpolymers comprise, in polymerized form,C2 (ethylene), at least one α-olefin and a diene. Suitable examples ofα-olefins include the C3-C20 α-olefins. Suitable examples of suitabledienes include the C4-C40 non-conjugated dienes.

The α-olefin is preferably a C3-C20 α-olefin, preferably a C3-C16α-olefin, and more preferably a C3-C10 α-olefin. Preferred C3-C10α-olefins are selected from the group consisting of propylene, 1-butene,1-hexene and 1-octene, and more preferably propylene. In a preferredembodiment, the interpolymer is an EPDM interpolymer. In a furtherembodiment, the diene is 5-ethylidene-2-norbornene (ENB).

In one embodiment, the diene is a C6-C15 straight chain, branched chainor cyclic hydrocarbon diene. Illustrative non-conjugated dienes arestraight chain acyclic dienes, such as 1,4-hexadiene and 1,5-heptadiene;branched chain acyclic dienes, such as 5-methyl-1,4-hexadiene,2-methyl-1,5-hexadiene, 6-methyl-1,5-heptadiene, 7-methyl-1,6-octadiene,3,7-dimethyl-1,6-octadiene, 3,7-dimethyl-1,7-octadiene,5,7-dimethyl-1,7-octadiene, 1,9-decadiene, and mixed isomers ofdihydromyrcene; single ring alicyclic dienes such as 1,4-cyclohexadiene,1,5-cyclooctadiene and 1,5-cyclododecadiene; multi-ring alicyclic fusedand bridged ring dienes, such as tetrahydroindene, methyltetrahydroindene; alkenyl, alkylidene, cycloalkenyl and cycloalkylidenenorbornenes such as 5-methylene-2-norbornene (MNB),5-ethylidene-2-norbornene (ENB), 5-vinyl-2-norbornene,5-propenyl-2-norbornene, 5-isopropylidene-2-norbornene,5-(4-cyclopentenyl)-2-norbornene, and 5-cyclohexylidene-2-norbornene.The diene is preferably a non-conjugated diene selected from ENB,dicyclopentadiene, 1,4-hexadiene, or 7-methyl-1,6-octadiene, andpreferably, ENB, dicyclopentadiene or 1,4-hexadiene, more preferably ENBor dicyclopentadiene, and even more preferably ENB.

Some examples of ethylene/α-olefin/diene interpolymers include theNORDEL IP Hydrocarbon Rubbers from The Dow Chemical Company.

In one embodiment, the ethylene/α-olefin/diene interpolymer comprises amajority amount of polymerized ethylene, based on the weight of theinterpolymer.

In one embodiment of the invention, the ethylene/α-olefin/dieneinterpolymer has a molecular weight distribution (Mw/Mn) from 2.0 to8.0, further from 2.0 to 5.0 and more further from 2.0 to 4.0, and evenmore further from 2.0 to 3.5. In a further embodiment, the interpolymeris an EPDM terpolymer. In a further embodiment, the diene is ENB.

In one embodiment, the ethylene/α-olefin/diene interpolymer has a Mooneyviscosity, ML(1+4) at 125° C., greater than 5, further greater than 10,and further greater than 15. In a further embodiment, the interpolymeris an EPDM terpolymer. In a further embodiment, the diene is ENB.

In one embodiment, the ethylene/α-olefin/diene interpolymer has a Mooneyviscosity, ML(1+4) at 125° C., less than 70, further less than, or equalto, 60, and further less than, or equal to, 50. In a further embodiment,the interpolymer is an EPDM terpolymer. In a further embodiment, thediene is ENB.

Mooney viscosity is that of the neat interpolymer (or calculatedviscosity of neat polymer for polymers that contain a filler, such ascarbon black, and/or an oil). The neat polymer refers to the polymerwithout filler and without oil.

In one embodiment, the ethylene/α-olefin/diene interpolymer has apolyene content from 0.5 to 5 weight percent, based on the weight of theinterpolymer. In a further embodiment, the interpolymer is an EPDMterpolymer. In a further embodiment, the diene is ENB.

In one embodiment, the ethylene/α-olefin/diene interpolymer has adensity greater than, or equal to, 0.850 g/cc, further greater than, orequal to, 0.855 g/cc, and further greater than, or equal to, 0.860 g/cc.In a further embodiment, the interpolymer is an EPDM terpolymer. In afurther embodiment, the diene is ENB.

In one embodiment, the ethylene/α-olefin interpolymer/diene has adensity less than, or equal to, 0.867 g/cc, further less than, or equalto, 0.865 g/cc, and further less than, or equal to, 0.863 g/cc. In afurther embodiment, the interpolymer is an EPDM terpolymer. In a furtherembodiment, the diene is ENB.

In one embodiment, the ethylene/α-olefin/diene interpolymer has a Mnfrom 10,000 to 250,000 g/mole, further from 10,000 to 75,000 g/mole. Ina further embodiment, the interpolymer is an EPDM terpolymer. In afurther embodiment, the diene is ENB.

In one embodiment, the ethylene/α-olefin/diene interpolymer has a Mwfrom 100,000 to 500,000 g/mole, further from 100,000 to 150,000 g/mole.In a further embodiment, the interpolymer is an EPDM terpolymer. In afurther embodiment, the diene is ENB.

An ethylene/α-olefin/diene interpolymer, and further a terpolymer, maycomprise a combination of two or more embodiments as described herein.

An ethylene/propylene/diene interpolymer, and further an EPDMterpolymer, may comprise a combination of two or more embodiments asdescribed herein.

Ethylene/α-Olefin Multi-Block Interpolymers (Component B)

In one embodiment, the second polymer is an ethylene/α-olefinmulti-block interpolymer, and further an ethylene/α-olefin multi-blockcopolymer. See above discussion on “Ethylene/α-Olefin Multi-BlockInterpolymers (Component A)” for applicable embodiments, other thanthose discussed in this section.

In one embodiment, the ethylene/α-olefin multi-block interpolymer, andfurther copolymer, has a density of less than, or equal to, 0.867 g/cc,further less than, or equal to, 0.866 g/cc, further less than, or equalto, 0.865 g/cc.

In one embodiment, the ethylene/α-olefin multi-block interpolymer, andfurther copolymer, has a density greater than, or equal to, 0.850 g/cc,further greater than, or equal to, 0.855 g/cc, and further greater than,or equal to, 0.860 g/cc. Density is measured by the procedure of ASTMD-792-08.

In one embodiment, the ethylene/α-olefin multi-block interpolymer, andfurther copolymer, has a melting point of greater than 90° C., furthergreater than 100° C. The melting point is measured by DifferentialScanning calorimetry (DSC) method described in U.S. Publication2006/0199930 (WO 2005/090427), incorporated herein by reference.

In one embodiment, the ethylene/α-olefin multi-block interpolymer, andfurther copolymer, has a melt index (I2) greater than, or equal to, 0.1g/10 min, further greater than, or equal to, 0.4 g/10 min, and furthergreater than, or equal to, 1 g/10 min, as determined using ASTM D-1238(190° C., 2.16 kg load).

In one embodiment, the ethylene/α-olefin multi-block interpolymer, andfurther copolymer, has a melt index (I2) less than, or equal to, 20 g/10min, further less than, or equal to, 10 g/10 min, and further less than,or equal to, 5 g/10 min, as determined using ASTM D-1238 (190° C., 2.16kg load).

An ethylene/α-olefin multi-block interpolymer may comprise a combinationof two or more embodiments as described herein.

An ethylene/α-olefin multi-block copolymer may comprise a combination oftwo or more embodiments as described herein.

Crosslinking Agents

Suitable crosslinking agents include, but are not limited to, peroxides.Peroxides include, but are not limited to, di-tertbutyl peroxide,tertbutylcumyl peroxide, dicumyl peroxide,2,5-dimethyl-2,5-di-(tertbutylperoxy)hexane,di-(tertbutylperoxyisopropyl)benzene, tertbutyl peroxybenzoate, and1,1-di-(tertbutylperoxy)-3,3,5-trimethylcyclohexane.

In one embodiment, the crosslinking agent is selected from peroxides.

In one embodiment, the crosslinking agent is present in an amount from0.5 to 5.0 parts by weight, further from 0.5 to 1.0 parts by weight,based upon 100 parts of the polymers in the composition.

Crosslinking temperatures and time employed are typical. Temperaturesranging from about 120° C. to about 225° C., and times ranging fromabout one minute to about 60 minutes can be used.

A crosslinking agent may comprise a combination of two or moreembodiments as described herein.

Foaming Agents

Foaming agents can be blends of two or more foaming agents. Foamingagents can be applied in both batch and continuous foaming processes.Foaming agents (i.e. blowing agent) used in the foam include, but arenot limited to, physical blowing agent and chemical blowing agent.

Physical blowing agents include pentanes, hexanes, heptanes, benzene,toluene, dichloromethane, trichloromethane, trichloroethylene,tetra-chloromethane, 1,2-dichloroethane, trichlorofluoromethane,1,1,2-trichlorotrifluoroethane, methanol, ethanol, 2-propanol, ethylether, isopropyl ether, acetone, methyl ethyl ketone, and methylenechloride; isobutene and n-butane, 1,1-difluoroethane. Chemical blowingagents include sodium bicarbonate, dinitrosopentamethylene-tetramine,sulfonyl hydrazides, azodicarbonamide, p-toluenesulfonyl semicarbazide,5-phenyltetrazole, diisopropyl-hydrazodicarboxylate,5-phenyl-3,6-dihydro-1,3,4-oxadiazin-2-one, and sodium borohydride.

Additives

In one embodiment, an inventive composition comprises at least oneadditive. Suitable additives include, but are not limited to, fillers,antioxidants, UV stabilizers, flame retardants, colorants or pigments,zinc oxide, stearic acid, zinc stearate, mold release agents, andcombinations thereof.

In one embodiment, the composition comprises at least one filler. In afurther embodiment, the filler is selected from carbon black, talc,calcium carbonate, clay or combinations thereof. In one embodiment, thefiller is present in an amount less than, or equal to, 50 weightpercent, further less than, or equal to, 20 weight percent, and furtherless than, or equal to, 10 weight percent, based on the weight of thecomposition. In one embodiment, the filler is present in an amountgreater than, or equal to, 1 weight percent, further greater than, orequal to, 2 weight percent, and further greater than, or equal to, 5weight percent based on the weight of the composition. In oneembodiment, the filler is present in an amount from 1 to 50 weightpercent, further from 2 to 20 weight percent, further from 5 to 10weight percent, based on the weight of the composition.

Antioxidants include, but are not limited to, hindered phenols,bisphenols, and thiobisphenols; substituted hydroquinones;tris(alkylphenyl)phosphites; dialkylthiodipropionates;phenylnaphthylamines; substituted diphenylamines; dialkyl, alkyl aryl,and diaryl substituted p-phenylene diamines; monomeric and polymericdihydroquinolines;2-(4-hydroxy-3,5-t-butylaniline)-4,6-bis(octylthio)1,3,5-triazine;hexahydro-1,3,5-tris-β-(3,5-di-t-butyl-4-hydroxyphenyl)propionyl-s-triazine;2,4,6-tris(n-1,4-dimethylpentylphenylene-diamino)-1,3,5-triazine; andtris-(3,5-di-t-butyl-4-hydroxybenzyl)isocyanurate.

In one embodiment, the composition further comprises a polymer selectedfrom such as propylene-ethylene copolymers, EPR, SEBS, SBS, EVA, LDPE,LLDPE, EAA, EEA, EMA, EBA, or EMAA. In a further embodiment, thispolymer is present in an amount less than 20 weight percent, furtherless than 10 weight percent, and further less than 5 weight percent,based on the weight of the composition.

Applications

The invention also provides for an article comprising at least onecomponent formed from an inventive composition. Articles include, butare not limited to extruded profiles, foams, weather strips, belts,hoses, wire and cable jacketing, tubes, flooring materials, gaskets,molded goods, sheets, and extruded parts. Additional articles includefootwear components, sporting goods, automotive parts (for example,dashboards and window seals), computer parts, building materials,household appliances and toys.

Compositions may be formed into a finished article of manufacture by anyone of a number of conventional processes and apparatus. Illustrativeprocesses include, but are not limited to, extrusion, calendaring,injection molding, compression molding, and other typical processesknown in the art. For example, articles can be prepared by injectionmolding, extrusion, extrusion followed by thermoforming, low pressuremolding, compression molding, bun foam process, and the like.

The inventive compositions are ideally suited for footwear and sportinggood applications, where good cushioning is required at a wide range oftemperatures.

DEFINITIONS

Unless stated to the contrary, implicit from the context, or customaryin the art, all parts and percents are based on weight, and all testmethods are current as of the filing date of this disclosure.

The term “composition,” as used herein, includes a mixture of materialswhich comprise the composition, as well as reaction products anddecomposition products formed from the materials of the composition.

The term “polymer,” as used herein, refers to a polymeric compoundprepared by polymerizing monomers, whether of the same or a differenttype. The generic term polymer thus embraces the term homopolymer (whichrefers to polymers prepared from only one type of monomer with theunderstanding that trace amounts of impurities can be incorporated intothe polymer structure), and the term interpolymer as definedhereinafter. Trace amounts of impurities, for example, catalystresidues, may be incorporated into and/or within the polymer.

The term “interpolymer,” as used herein, refers to polymers prepared bythe polymerization of at least two different types of monomers. Thegeneric term interpolymer thus includes copolymers (employed to refer topolymers prepared from two different types of monomers), and polymersprepared from more than two different types of monomers.

The term, “olefin-based polymer,” as used herein, refers to a polymerthat comprises, in polymerized form, a majority amount of olefinmonomer, for example ethylene or propylene (based on the weight of thepolymer), and optionally may comprise one or more comonomers.

The term, “ethylene-based polymer,” as used herein, refers to a polymerthat comprises, in polymerized form, a majority amount of ethylenemonomer (based on the weight of the polymer), and optionally maycomprise one or more comonomers.

The term, “ethylene/α-olefin interpolymer,” as used herein, refers to aninterpolymer that comprises, in polymerized form, a majority amount ofethylene monomer (based on the weight of the interpolymer), and at leastone α-olefin. As used in the context of this disclosure,ethylene/α-olefin interpolymer excludes ethylene/α-olefin multi-blockinterpolymers.

The term, “ethylene/α-olefin copolymer,” as used herein, refers to acopolymer that comprises, in polymerized form, a majority amount ofethylene monomer (based on the weight of the copolymer), and anα-olefin, as the only two monomer types. As used in the context of thisdisclosure, ethylene/α-olefin copolymer excludes ethylene/α-olefinmulti-block copolymers.

The term, “propylene-based polymer,” as used herein, refers to a polymerthat comprises, in polymerized form, a majority amount of propylenemonomer (based on the weight of the polymer), and optionally maycomprise one or more comonomers.

The term, “propylene/α-olefin interpolymer,” as used herein, refers toan interpolymer that comprises, in polymerized form, a majority amountof propylene monomer (based on the weight of the interpolymer), and atleast one α-olefin.

The term, “propylene/α-olefin copolymer,” as used herein, refers to acopolymer that comprises, in polymerized form, a majority amount ofpropylene monomer (based on the weight of the copolymer), and anα-olefin, as the only two monomer types.

The term, “propylene/ethylene interpolymer,” as used herein, refers toan interpolymer that comprises, in polymerized form, a majority amountof propylene monomer (based on the weight of the interpolymer), andethylene.

The term, “propylene/ethylene copolymer,” as used herein, refers to acopolymer that comprises, in polymerized form, a majority amount ofpropylene monomer (based on the weight of the copolymer), and ethylene,as the only two monomer types.

The terms “comprising,” “including,” “having,” and their derivatives,are not intended to exclude the presence of any additional component,step or procedure, whether or not the same is specifically disclosed. Inorder to avoid any doubt, all compositions claimed through use of theterm “comprising” may include any additional additive, adjuvant, orcompound, whether polymeric or otherwise, unless stated to the contrary.In contrast, the term, “consisting essentially of” excludes from thescope of any succeeding recitation any other component, step orprocedure, excepting those that are not essential to operability. Theterm “consisting of” excludes any component, step or procedure notspecifically delineated or listed.

Test Methods

Density

Polymer density was measured in accordance with ASTM D-792.

Melt Index

Melt index (I2) of an ethylene-based polymer is measured in accordancewith ASTM D-1238, condition 190° C./2.16 kg. Melt index (I5) of anethylene-based polymer is measured in accordance with ASTM D-1238,condition 190° C./5.0 kg. Melt index (110) of an ethylene-based polymeris measured in accordance with ASTM D-1238, condition 190° C./10.0 kg.High load melt index (121) of an ethylene-based polymer is measured inaccordance with ASTM D-1238, condition 190° C./21.0 kg. Forpropylene-based polymers, the melt flow rate (MFR) is measured inaccordance with ASTM D-1238, condition 230° C./2.16 kg.

Differential Scanning Calorimetry (DSC)

Differential Scanning calorimetry (DSC) is used to measure crystallinityin ethylene-based (PE) samples and propylene-based (PP) samples. About 5to 8 mg of film sample is weighed and placed in a DSC pan. The lid iscrimped on the pan to ensure a closed atmosphere. The sample pan isplaced in a DSC cell, and then heated, at a rate of approximately 10°C./min, to a temperature of 180° C. for PE (230° C. for PP). The sampleis kept at this temperature for three minutes. Then the sample is cooledat a rate of 10° C./min to −60° C. for PE (−40° C. for PP), and keptisothermally at that temperature for three minutes. The sample is nextheated at a rate of 10° C./min, until complete melting (second heat).The percent crystallinity is calculated by dividing the heat of fusion(H_(f)), determined from the second heat curve, by a theoretical heat offusion of 292 J/g for PE (165 J/g, for PP), and multiplying thisquantity by 100 (for example, % cryst.=(H_(f)/292 J/g)×100 (for PE)).

Unless otherwise stated, melting point(s) (T_(m)) of each polymer isdetermined from the second heat curve, and the crystallizationtemperature (T_(c)) is determined from the first cooling curve.

Mooney Viscosity of Polymer

Polymer Mooney Viscosity (ML1+4 at 125° C.) is measured in accordancewith ASTM 1646-04, with a one minute preheat time and a four minuterotor operation time. The instrument is an Alpha Technologies RheometerMDR 2000.

Gel Permeation Chromatography

The chromatographic system consisted of either a Polymer LaboratoriesModel PL-210 or a Polymer Laboratories Model PL-220. The column andcarousel compartments were operated at 140° C. The columns were threePolymer Laboratories, 10-micron Mixed-B columns. The solvent used was1,2,4 trichlorobenzene. The samples were prepared at a concentration of“0.1 gram of polymer in 50 milliliters of solvent.” The solvent used toprepare the samples contained “200 ppm of butylated hydroxytoluene(BHT).” Samples were prepared by agitating lightly for two hours at 160°C. The injection volume was 100 microliters, and the flow rate was 1.0milliliters/minute.

Calibration of the GPC column set was performed with 21 “narrowmolecular weight distribution polystyrene standards,” with molecularweights ranging from 580 to 8,400,000, arranged in six “cocktail”mixtures, with at least a decade of separation between individualmolecular weights. The standards were purchased from PolymerLaboratories (Shropshire, UK). The polystyrene standards were preparedat “0.025 grams in 50 milliliters of solvent” for molecular weightsequal to, or greater than, 1,000 kg/mol, and “0.05 grams in 50milliliters of solvent” for molecular weights less than 1,000 kg/mol.The polystyrene standards were dissolved at 80 degrees Celsius, withgentle agitation, for 30 minutes. The narrow standards mixtures were runfirst, and in order of decreasing “highest molecular weight” componentto minimize degradation. The polystyrene standard peak molecular weightswere converted to polyethylene molecular weights using the followingequation: M_(polyethylene)=A×(M_(polystyrene))^(B), where M is themolecular weight, A has a value of 0.431 and B is equal to 1.0 (asdescribed in Williams and Ward, J. Polym. Sc., Polym. Let., 6, 621(1968)). Polyethylene equivalent molecular weight calculations wereperformed using Viscotek TriSEC software Version 3.0.

Compression Set

Compression Set (CS) was measured on the foam sample according to ASTMD395 The Compression Set was calculated as the percentage of theoriginal deflection, measured after the material was allowed to recoverat standard conditions for 30 minutes. Percent Compression Set wascalculated using the formula: C=[(h₀−h_(i))/(h₀−h_(n))]×100, where h₀ isthe original specimen thickness, h_(i) is the specimen thickness aftertesting, and h_(n) is the spacer thickness.

Mechanical Properties

Tensile and elongation were measured in accordance with ASTM D412, usingphylon foam. Tear strength and split tear were measured in accordancewith ASTM D624 and BS 5131, respectively, using phylon foam.

Hardness

Hardness of the foam was measured in accordance with ASTM D2240, usingphylon foam.

Rebound

Rebound of the foam was measured in accordance with ASTM D2632, usingphylon foam.

Foam Density

Density of the foam was measured in accordance with ASTM D297, usingphylon foam.

Shrinkage

Shrinkage was measure on a foam specimen with dimension of “10 cm by 10cm by 10 mm” Two lines with a length of 10 cm were diagonally drawn onthe foam specimen prior placing into the oven. The specimens were placedin an oven at 70° C. for 40 minutes. Then the foams were taken out ofthe oven, and placed on a rack to cool under constant humidity andtemperature (23° C., 50% relative humidity) for 30 minutes. The lineswere measured again, and the percent the shrinkage was determined asfollows: Shrinkage (%)=(initial length−final length)/(initiallength)×100%

The following examples illustrate, but do not, either explicitly or byimplication, limit the present invention.

EXPERIMENTAL

Components used in the compositions of this study are shown in Table 1below, and the compositions are shown in Table 2 below.

TABLE 1 Components Density 12 Tm Components Suppliers (g/cc) (g/10 min)(° C.) ENGAGE 8440 Dow Chemical Company 0.897 1.6 93 INFUSE 9530 DowChemical Company 0.887 5 119 INFUSE 9107 Dow Chemical Company 0.866 1121 ENGAGE 8180 Dow Chemical Company 0.863 0.5 47 NORDEL Dow ChemicalCompany 0.86 IP 3430* Zinc oxide Aldrich Stearic acid Zinc StearateDicumyl AKZO NOBEL peroxide CaCO3 AA110 TAIHSIN Chemical Ind.(azodicarbon- Co. Ltd amide) *Mooney Viscosity = 27 (ML 1 + 4 at 125°C.)

TABLE 2 Compositions Formulation (phr, based on sum weight Ex- Ex- Ex-Ex- Ex- of polymer ample ample ample ample ample components) 1 2 3 4 5ENGAGE 8440 70 70 70 0 0 INFUSE 9530 0 0 0 40 70 INFUSE 9107 30 0 0 0 0ENGAGE 8180 0 30 0 0 0 NORDEL IP 3430 0 0 30 60 30 Zinc oxide 1.5 1.51.5 1.5 1.5 Stearic acid 0.5 0.5 0.5 0.5 0.5 Zinc Stearate 1 1 1 1 1Dicumyl peroxide 0.85 0.85 0.85 0.85 0.85 CaCO3 5 5 5 5 5 AA110 3.1 3.13.1 3.1 3.1 (azodicarbonamide)Foams

Polymer components were compounded with other additives, foaming agents,etc. (formulations shown in Table 2), using an internal kneader. Theresulted compounds were converted into foams by compression molding atmold temperature of 160° C. The foamed material was cooled, and cut intorequired shape (known as perform). The pre-form was compressed in a moldto about ⅔ of its original size in a heated mold. After heating, themold was cooled to room temperature, where the foam sets its shape.Properties of the foams are shown in Table 3.

TABLE 3 Formulation Test Example Example Example Example Example (phr)Method 1 2 3 4 5 Asker C ASTM 54~55 55~56 59~60 52~53 53~54 (skin on)D2240 Density (g/cm3) ASTM 0.2001 0.2195 0.3193 0.3785 0.2662 D297Tensile [kg/cm2] ASTM 45.8 47.2 32.4 23.9 26.8 D412 Elongation [%] ASTM304.2 299.2 298.8 377.6 296.5 D412 Type C Tear ASTM 19.2 18.1 15.5 11.413.1 [kg/cm] D624 Split Tear BS 3.6 3.4 3.4 2.3 2.3 [kg/cm] 5131 Rebound(%) ASTM 46 48 51 61 56 D2632 Comp Set 50%, ASTM 31.1 28.1 19.1 9.6 23.650° C./6 hr (%) D395 Shrinkage, 40 0.69 0.25 1.18 0.69 0.69 min, 70° C.(%)Comparative Foams

Comparative foams formed from PU and EVA, and used for midsoleapplications, are shown in Table 4 below.

TABLE 4 Comparative Foams Comparative Comparative Ex. A Ex. B PropertiesTest Method (EVA) (PU) Asker Skin (skin on) ASTM D2240 51-53 55-57Density (g/cc) ASTM D297 0.24 0.35 Tensile (kg/cm²) ASTM D412 29.8 41.1Elongation (%) ASTM D412 323 341 Tear Strength ASTM D624 11.4 12.9(kg/cm) Split Tear (kg/cm) BS 5131 3.1 2.9 Rebound (%) ASTM D2632 54 31Compression Set ASTM D395 57.6 11.1 50%, 50° C./6 h [%] Shrinkage 4.1 040 min, 70° C. [%]

Applicants have unexpectedly discovered that their inventivecompositions generate foams that have better “consistent temperaturebehavior,” as compared to incumbent EVA and PU foams. FIG. 1 showsdynamic properties of both the comparative and inventive foams analyzedusing a “T.A. RSA III Rheometer,” equipped with “25 mm parallel plates,”in compressive mode. The test conditions were −20° C. to 60° C., at 2°C./min, 1 hertz. The profiles in FIG. 1 show that storage modulus, E′ ofall the inventive foams remain relatively constant from −20° C. to 35°C. For the inventive Examples 4 and 5 there is no significant change inthe E′ value with temperature. For Inventive Examples 4, the ratio ofthe storage modulus at −20° C., E′ (−20° C.), to the storage modulus at35° C., E′(−35° C.), is in not more than 1:1. The inventive examples(foams) had less, or no change in, stiffness/hardness, as compared tothe EVA foams. The profiles of FIG. 1 also show that the E′ value of thePU foam increases dramatically with decreasing temperature, as comparedto the inventive foams. As seen from Tables 3 and 4, Inventive Example 5had an overall better balance of properties (i.e. good resilience(Rebound) and excellent compression set) compared to ComparativeExamples 1 and 2.

The inventive foams had more consistent temperature behavior than theincumbent EVA and PU foams. Compared to the EVA-based foam, theinventive foams better compression set (below 35%), at comparable foamdensities. Compared to the PU-based foam, the inventive foams havebetter resilience at comparable densities. The inventive foams are alsomore cost effective to produce, have better hydrolysis resistant, andbetter recyclability compared to the PU-based foam.

It has been discovered that the inventive compositions generate foamswith consistent dynamic properties over a broad range of temperature,and an elastic relaxation (measured as compression set @ 50 C) lowerthan 40%, which makes these compositions better than the incumbent EVA-and PU-based for foams that are subject to greater temperature extremes.These properties features lead to improved foams with improveddurability, cushioning and comfort. The inventive compositions areespecially suitable for use in footwear and sporting good applications,and other applications that require good cushioning effect in coldenvironments.

The invention claimed is:
 1. A composition comprising the following: A)a first polymer selected from the following: i) an ethylene/α-olefininterpolymer; or ii) an ethylene/α-olefin multi-block interpolymer; B) asecond polymer selected from the following: iii) an ethylene/α-olefininterpolymer; iv) an ethylene/α-olefin/non-conjugated dieneinterpolymer; or v) an ethylene/α-olefin multi-block interpolymer; andwherein the first polymer has a density from 0.880 to 0.910 g/cc, andthe second polymer has a density less than, or equal to, 0.867 g/cc, andwherein the weight ratio of the first polymer to the second polymer isfrom 0.5 to
 9. 2. The composition of claim 1, wherein the first polymerhas a melting temperature (Tm) greater than 70° C., as determined byDSC.
 3. The composition of claim 1, wherein the first polymer has amelting temperature (Tm) less than 130° C., as determined by DSC.
 4. Thecomposition of claim 1, wherein the first polymer has a molecular weightdistribution (Mw/Mn) from 1.2 to
 3. 5. The composition of claim 1,wherein the first polymer is i) an ethylene/α-olefin interpolymer. 6.The composition of claim 5, wherein the first polymer is a homogeneouslybranched linear ethylene/α-olefin interpolymer, or a homogeneouslybranched substantially linear ethylene/α-olefin interpolymer.
 7. Thecomposition of claim 1, wherein the first polymer is ii) an olefin blockinterpolymer.
 8. The composition of claim 1, wherein the second polymerhas a molecular weight distribution (Mw/Mn) from 1.2 to
 3. 9. Thecomposition of claim 1, wherein the second polymer is iii) anethylene/α-olefin interpolymer.
 10. The composition of claim 9, whereinthe ethylene/α-olefin interpolymer is a homogeneously branched linearethylene/α-olefin interpolymer, or a homogeneously branchedsubstantially linear ethylene/α-olefin interpolymer.
 11. The compositionof claim 1, wherein the second polymer is iv) anethylene/α-olefin/non-conjugated diene interpolymer.
 12. The compositionof claim 11, wherein the ethylene/α-olefin/non-conjugated dieneinterpolymer has a Mooney Viscosity (ML 1+4) at 125° C., from 5 to 70.13. The composition of claim 1, wherein the composition furthercomprises a free radical agent and a foaming agent.
 14. A foam formedfrom the composition of claim
 1. 15. An article comprising at least onecomponent formed from the composition of claim 1.